CN101688329B - Method for manufacturing fine polymer - Google Patents

Method for manufacturing fine polymer Download PDF

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Publication number
CN101688329B
CN101688329B CN2008800240188A CN200880024018A CN101688329B CN 101688329 B CN101688329 B CN 101688329B CN 2008800240188 A CN2008800240188 A CN 2008800240188A CN 200880024018 A CN200880024018 A CN 200880024018A CN 101688329 B CN101688329 B CN 101688329B
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China
Prior art keywords
polymer
outlet
nanofiber
superheated steam
fine
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CN2008800240188A
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Chinese (zh)
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CN101688329A (en
Inventor
高桥光弘
竹泽干夫
富永善章
黑川崇裕
住田宽人
石川和宜
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

A method for manufacturing a fine polymer including: generating superheated steam by a superheated steam generating unit (101); adjusting the pressure of the generated superheated steam by a pressure adjusting unit (102); receiving a polymer by a reception unit (103); heating the received polymer to a predetermined temperature by a heating unit (104); discharging the heated polymer through a first discharge port (111); and discharging the superheated steam through a second discharge port (121) at the same time as the time when the heated polymer is discharged. Here, the second discharge port (121) surrounds the first discharge port (111), and the first discharge port (111) and the second discharge port (121) face the same direction.

Description

The manufacturing approach of fine polymer
Technical field
The present invention relates to a kind of method and a kind of fine polymer manufacturing equipment that is used to make meticulous swelling (swelled) polymer; Be particularly related to the manufacturing approach of the meticulous swelling polymer that a kind of manufacturing nanofiber (nanofiber) product uses, and the fine polymer manufacturing equipment.
Background technology
Electricity spinning (electrospinning) method is a kind of known method that is used to make filamentary material, and this material comprises polymer, and has the diameter (below be called nanofiber) of submicron-scale.
Electrical spinning method is a kind of method that produces nanofiber through following mode: the needle nozzle through equipment sprays (perhaps make polymer solution flow) with polymer solution towards gatherer (passive electrode).Polymer solution contains solvent and is dispersed in the polymer in the solvent with particle form, and nozzle is applied in high pressure.
In electrical spinning method, high pressure is applied to nozzle, thereby at first charged to the polymer solution in the predetermined space through nozzle ejection.Along with the solvent evaporation, the charge density that contains the polymer solution of the polymer particles that in air, flies increases.When the Coulomb force along the repulsion direction that in polymer solution, produces surpassed the surface tension of polymer solution, the polymer particles in the polymer solution was pulled into wire consumingly.This phenomenon is called " electrostatic burst ".This electrostatic burst sequentially occurs in the predetermined space, produces nanofiber, contains the fine polymer particulate with sub-micron diameter.
In addition; Nanofiber through utilizing said method to produce is deposited in the substrate; Can produce film, and through nanofiber is deposited in the substrate, the thickness of nano-fiber film is greater than film in process with tridimensional network; Can make highly porous silk screen (web) (bondedfibre fabric), have the network structure of submicron-scale.
Utilize the highly porous fabric of electrical spinning method manufacturing to have the hole of nanometer scale, and have the same big surface with whole fabric.Therefore, highly porous fabric can be applicable to the separator in filter, the battery, the polymer dielectric that is used for battery, electrode etc., and high-performance is provided.
Through utilizing the inwardly projecting orifice of parallel setting; Existing equipment makes a large amount of nanofibers be deposited on the sedimentation unit; And according to the method that is used to produce a large amount of nanofibers; The highly porous fabric that completion is processed by nanofiber is to make the highly porous fabric (as an example, seeing patent citation) of the reality of being processed by nanofiber.
Equipment applies 5KV or bigger high pressure between nozzle and gatherer, and or ground, with gatherer ground connection, perhaps applying voltage to gatherer, this voltage has and the voltage antipole property that is applied to nozzle, and produces nanofiber.
Patent citation 1: Japanese Unexamined Patent Application is open: No.2002-201559
Summary of the invention
As stated, a kind of original solution that is used for producing nanofiber is to obtain at solvent through the polymer dissolution (perhaps disperseing) with particle form.As solvent, organic solvent is with in many cases.The organic solvent that comprises in the original solution evaporates in the process that produces nanofiber, and therefore must give people and environment with sufficient consideration in selection with an organic solvent.For example, the nanofiber product manufacturing device need be installed in the space of sealing,, collect the organic solvent of evaporation perhaps as prevention.
In using the situation of flammable organic solvent, be used to prevent that the precautionary measures of exploding from must adopt for the nanofiber product manufacturing device.
Therefore, inevitably very complicacy and size are big for existing nanofiber product manufacturing device, have increased manufacturing cost and space cost.
In addition, organic solvent need be up to 50-95% with respect to the weight ratio of original solution, and therefore needs a large amount of organic solvents to produce the nanofiber of scheduled volume.The cost of organic solvent is the principal element that totle drilling cost increases.
Thereby the present invention proposes to address the above problem, and target provides a kind of method that is used to make fine polymer, fine polymer manufacturing equipment and be used to make the method for nanofiber product, and the nanofiber product manufacturing device all is safe and cheap.
In order to realize above-mentioned target, according to the present invention, be used to make the method for the fine polymer that comprises meticulous swelling polymer particles, comprising: produce superheated steam through the superheated steam generation unit; Regulate the pressure of the superheated steam that is produced through pressure regulating unit; Receive polymer through receiving element; Through heating unit the polymer that receives is heated to predetermined temperature; Discharge the polymer of heating through first outlet; And discharge said superheated steam through second outlet, be discharged from simultaneously with the polymer that heats.Here, second outlet is around first outlet, and first outlet and second outlet are towards equidirectional.
According to this method, can make trickleer polymer particles and in solvent swelling polymer in the water for example, collect the meticulous swelling particulate of fine polymer, and make and have low viscous fine polymer.
In addition, the method that is used to make fine polymer can comprise makes that the fine polymer of discharge is supplied with receiving element again when fine polymer is discharged from.
Utilize this structure, can make the meticulousr particulate of polymer, and in solvent repeatedly swelling polymer particulates in the water for example, even thereby fine polymer becomes.
When above-mentioned polymer is used to make nanofiber, can be safely and produce nanofiber at an easy rate.
In order to realize above-mentioned target, fine polymer manufacturing equipment according to the present invention comprises: the superheated steam generation unit is configured to produce superheated steam; Pressure regulating unit is configured to regulate the pressure of the superheated steam of generation; Receiving element is used to receive polymer; Heating unit is configured to the polymer that receives is heated to predetermined temperature; First outlet, the polymer of heating is through its discharge; With second outlet, superheated steam is through its discharge.Here, second outlet is around first outlet, and first outlet and second outlet are towards equidirectional.
As above, the fluid through a discharge in these two outlets is a superheated steam, and this makes can heat and make trickleer polymer particles, and passes through mixing water molecule between the polymer molecule in polymer particles, with the polymer particles swelling.
In addition, the present invention can be implemented as a kind of nanofiber product manufacturing device, comprising: receiving element is used to receive polymer; Heating unit is configured to polymer is heated to predetermined temperature; First outlet, the polymer of heating is through its discharge; With second outlet, the fluid that comprises water is through its discharge, and second outlet is around first outlet, and first and second outlets are towards equidirectional, and the electric charge supplying electrode is applied to electric charge the polymer of heating when the polymer of heating is discharged; Passive electrode is collected the nanofiber that sprays through spray-hole; And power supply, be used for applying between electrode and the passive electrode and produce electric field at electric charge.
Utilize this structure, can produce the trickle polymer that contains meticulous swelling polymer particles, and produce nanofiber safely and easily through causing a series of electrostatic bursts.
Utilize the present invention, can fine polymer be provided easily, comprise meticulous swelling polymer particles,, be used to produce nanofiber as original material.In addition, when fine polymer is used to produce nanofiber, can be safely and produce nanofiber at an easy rate.
The Japanese patent application No.2007-182365 that on July 11st, 2007 submitted to discloses, and comprises specification, accompanying drawing and claim, draws in this integral body to be reference.
Description of drawings
Through following description, in conjunction with accompanying drawing, of the present invention these are incited somebody to action obviously with other target, advantage and characteristic, and accompanying drawing shows specific embodiment of the present invention.
Fig. 1 is the cutaway view according to fine polymer manufacturing equipment of the present invention.
The conceptual view of Fig. 2 shows the particulate of the amplification of polymer.
Fig. 3 is the notion perspective view of bondedfibre fabric manufacturing equipment, comprises the nanofiber product manufacturing device.
The figure of Fig. 4 shows the instance of injection unit and passive electrode.
Fig. 5 is the perspective view of the distortion of bondedfibre fabric manufacturing equipment.
Fig. 6 is the cutaway view of the distortion of fine polymer manufacturing equipment.
Fig. 7 is the cutaway view of fine polymer manufacturing equipment and nanofiber product manufacturing device, and they become whole each other.
Reference numerals list:
100 fine polymer manufacturing equipments
101 superheated steam generation devices
102 pressure-regulating devices
103 receiving magazines
104 heaters
105 power supplys
106 pumps
107 storage boxes
108 control device
109 thermometers
110 inwardly projecting orifices
111 first outlets
112 transfer paths
120 external nozzles
121 second outlets
122 ingates
130 diaxons are extruded device
131 hoppers
132 transport paths again
136 transfer pumps again
200 nanofiber product manufacturing devices
210 injection units
211 pipelines
212 spray-holes
213 nozzles
214 belt wheels
215 bands
216 rotating cylinders
217
218 motor
219 pedestals
220 passive electrodes
250 first power supplys
251 second sources
300 bondedfibre fabric manufacturing equipments
360 lamellas
370 supply units
400 nanofibers
400 polymer
410 bondedfibre fabrics.
The specific embodiment
(embodiment)
Describe below according to of the present invention that meticulous (fine, fine) the polymer manufacturing equipment 100.
Fig. 1 is the cutaway view of fine polymer (macromolecular material) manufacturing equipment 100 according to the present invention.
Like Fig. 1, fine polymer manufacturing equipment 100 comprises: superheated steam generation device 101, as the superheated steam generation unit; Pressure-regulating device 102 is as pressure regulating unit; Receiving magazine 103 is as receiving element; Heater 104 constitutes heating unit; Power supply 105 constitutes heating unit; Inwardly projecting orifice 110 has first outlet 111; External nozzles 120 has second outlet 121; Pump 106; Storage box 107; With control module 108.
Superheated steam generation device 101 comprises evaporimeter; It is that the saturated vapor generation device is used to produce saturated vapor; And can the saturated vapor that in evaporimeter, produces be heated to 100 degrees centigrade or higher under normal pressure, and can produce the superheated steam of normal pressure.Among this embodiment, suppose that the temperature with the superheated steam that is supplied is set to the arbitrary temp in 500 degrees centigrade.
Here, superheated steam representes to have the steam of the temperature that surpasses 100 degrees centigrade.In the present embodiment, term " superheated steam " expression H 2Steam in the O gas phase.
Be used to heat saturated vapour and comprise the method and the method that is used for heating saturated vapour that is used to utilize electric heater heating saturated vapour with the method that produces superheated vapor through combustion fuel.The method of using in the present embodiment is the method that is used for producing through following manner superheated vapor, ties up a plurality of metal tubes, utilizes the eddy current heating with the metal tube heating, and makes saturated vapour pass each metal tube.The power supply that is used for heating metal pipe is high frequency electric source (frequency that comprises 10KHz-60KHz is provided).
Pressure-regulating device 102 as pressure regulating unit is such devices, and its pressure with the superheated vapor with normal pressure that superheated vapor generation device 101 produces increases to predetermined pressure.The superheated vapor with predetermined pressure of discharging through second outlet 121 can be so that polymer particles be meticulousr, and in superheated vapor, makes the polymer particles swelling of discharging through first outlet 111.
Receiving magazine 103 is corresponding to receiving element, and polymer is fed to wherein, and polymer is stored in wherein.
Heater 104 is the electric heater around receiving magazine 103 as heating unit, the polymer of heating storage in receiving magazine 103, thus fully reduce and can discharge up to the viscosity of polymer through first outlet 111.
Power supply 105 as heating unit, provides electric energy to heater 104.The electric energy that is provided can be regulated arbitrarily.
First outlet 111 is opening portions, and polymer is discharged through it, and the temperature of this polymer raises through heating steam, and has the viscosity that reduces.First outlet 111 is positioned at the edge of inwardly projecting orifice 110, and this edge is the marginal portion of transfer path 112, and polymer is transmitted through transfer path.The diameter of transfer path 112 diminishes towards the marginal portion of inwardly projecting orifice 110.
Second outlet 121 is opening portions, and the superheated vapor that pressure increases through pressure-regulating device 102 is discharged through its, and has and center on the round-shaped of first outlet 111.Outer side nozzle 120 comprises second outlet 121 that is positioned at edge, has the cylinder body shape of placing with one heart with respect to inwardly projecting orifice 110.The opposite edge of second outlet 121 closely contacts and therefore sealing with the edge of transfer path 112.External nozzles 120 includes oral pore 122, has the superheated vapor that increases pressure and gets into through this ingate.It is whole that ingate 122 becomes with the part of the perisporium of external nozzles 120.
Pump 106 is used for the polymer pump of receiving magazine 103 is delivered to first outlet 111, and this polymer is reduced to predetermined value by heater 104 heating up to the viscosity of polymer.
Storage box 107 receives polymer, and this polymer contains the polymer particles of meticulous swelling, and the store aggregated thing is together with water.
Control device 108 is computers, is used for controlled pressure adjusting device 102, power supply 105 and pump 106 etc.Control device 108 is analyzed the data that obtain from thermometer 109 grades; And thereby the temperature and pressure through carrying out following FEEDBACK CONTROL telomerized polymer is to predetermined value: the pressure of the superheated vapor that increases through pressure-regulating device 102; Power supply 105 is applied to the electric energy of heater 104, by pressure of the polymer of pump 106 pumpings etc.
The method and the fine polymer manufacturing equipment 100 that are used to make fine polymer are described below.
At first, the polymer that is fit to is fed in the receiving magazine 103.Polymer can have any form, for example particle (pellet) form.Do not need to be used for by the numerical limitations of the polymer of feed polymer can to use multiple polymers to only a kind of.
The temperature that is fed to the polymer in the receiving magazine 103 increases to predetermined temperature through heater 104.The temperature of polymer is always utilized thermometer 109 inspections.Control device 108 monitor temperatures change, and control from the amount of the electric energy of power supply 105 supplies, thereby the temperature of polymer remains on predetermined temperature.
Next, when the temperature of judging polymer when control device 108 reaches predetermined temperature, control device 108 operating pumps 106, control pump 106 is with predetermined pressure pumping polymer.Like this, polymer is pumped into first outlet 111.
As above, polymer is discharged through first outlet 111 with predetermined pressure.
On the other hand, superheated vapor generation unit 101 produces the superheated vapor with predetermined temperature.Pressure-regulating device 102 is through control device 108 controls, increases to predetermined pressure with the pressure of the superheated vapor that will produce through superheated vapor generation device 110.
Superheated vapor with predetermined pressure is fed to outer side nozzle 120, and discharges through second outlet 121 around first outlet 111.
When superheated vapor was discharged through second outlet 121, polymer was discharged through first outlet 111.Effect below the nozzle that solution-air is mixed provides: the polymer with micro particles is sprayed.
Except the conduction heat effect, superheated vapor has high radiation heating effect, and has following effect: the polymer heating of discharging from first outlet 111, and the viscosity of reduction polymer.When polymer and heating steam were discharged simultaneously, polymer mixed with heating steam.The polymer that mixes with heating steam is heated, and be formed trickle in following degree up to polymer particles: the molecule in the polymer particulates is not destroyed.Like Fig. 2 b, hydrone is blended between the fine polymer molecule in the polymer particles 401 of polymer.Should be noted that Fig. 2 a shows polymer particles 401, contain polymer molecule, but do not contain the hydrone that is blended between the polymer molecule.
Above-mentioned solution-air mixing nozzle and superheated vapor provide following effect: make that the polymer particles 401 of polymer is trickleer, reach the 5-100 micron, and with polymer particles 401 in for example swelling in the water of solvent.Can the size of polymer particles 401 be changed to arbitrary dimension, for example 30 microns and 50 microns through regulating in following one or some: the temperature and pressure of superheated vapor, temperature of polymer (viscosity) and pressure.
At last, the fine polymer that contains meticulous swelling polymer particles is collected with superheated vapor, and the polymer that mixes with superheated vapor is stored in the storage box 107.
The polymer molecule of polymer of storage is dispersed in the water, as polymer by emulsification (perhaps accurate emulsification).
The said equipment and method make can make fine polymer, contains the polymer particles of meticulous swelling, and has low viscosity, needn't use any organic solvent simultaneously.In addition, fine polymer particulate 401 is separately convenient, because hydrone is blended between the fine polymer molecule, and the intermolecular power of the polymer molecule in the polymer particles 401 of polymer weakens.
Have another kind of method and be used to utilize the ultrasonic vibration polymer particles 401 of polymer that becomes more meticulous, but this method is brought a problem, ultrasonic vibration is divided into polymer molecule the low-molecular-weight molecule that has with the material different qualities.On the contrary, the said equipment and method can provide to be had low viscosity and as the polymer of polymer desirable characteristics, not to use any organic solvent, moving because the polymer molecule of the polymer of feed is kept perfectly.
The instance of polymer that can be used as polymer is following: polypropylene, polyethylene, polystyrene, PEO; PETG, polybutylene terephthalate (PBT) (polybutylene terephthalate), poly phthalate gathers a benzene terephthalate (poly-m-phenylene terephthalate); Gather to benzene M-phthalic acid (poly-p-phenylene isophthalate) polyvinylidene fluoride (polyvinylidenedifluorides), polyvinylidene fluoride-hexafluoropropylene copolymer (polyvinylidenedifluoride-hexafluoro propylene copolymer); Polyvinyl chloride, polyvinylidene chloride-ACR, polyacrylonitrile; Polyacrylonitrile-methacrylate ester copolymer, Merlon, poly-allylat thing (polyallylate); Polyestercarbonate, nylon, aromatic polyamides; Polycaprolactone, PLA (polylactric acid), polyglycolic acid; Collagen, Poly-(polyhydroxybutyric acid), polyvinyl acetate and polypeptide.The synthetic of the polymer that from listed polymer, obtains through any selection and feed polytype polymer can also be provided in addition.
Describe below and be used to utilize fine polymer to make the method for nanofiber product; This polymer contains the polymer particles that utilizes the meticulous swelling that the said equipment makes, and describes the nanofiber product manufacturing device, is used for through the nanofiber deposition that produces being made the method and the bondedfibre fabric manufacturing equipment of bondedfibre fabric.
Fig. 3 is the conceptual perspective view of bondedfibre fabric manufacturing equipment 300, comprises the nanofiber product manufacturing device.
Like Fig. 3, bondedfibre fabric manufacturing equipment 300 comprises: nanofiber product manufacturing device 200 comprises injection unit 210 and passive electrode 220; With deposition lamella 360, as sedimentation unit.Nano-fiber film in should be noted that polymer that mark 400 indication will be sprayed and handling, because they can not clearly distinguish each other, and the bondedfibre fabric accomplished of mark 410 indications.
Injection unit 210 is the devices with spray-hole, is used for spraying polymer (or make polymer flow), is used to produce nanofiber.First power supply 250 is applied to injection unit 210 with the electromotive force predetermined with respect to earth potential.
Injection unit 210 is connected to the storage box 107 and pipeline 211 that is used for the store aggregated thing, and through pipeline 211, the fine polymer that contains meticulous swelling polymer particles is provided with predetermined pressure.
Passive electrode 220 is connected to second source 251, thereby predetermined voltage is applied to injection unit 210, and collects the nanofiber 400 that produces.
Should be noted that first power supply 250 has injection unit 210 directly grounded functions with second source 251.What only need is: nanofiber product manufacturing device 200 produces electric field (power line) between injection unit 210 and passive electrode 220.Except directly applying electric charge with second source 251 from first power supply 250, give third electrode through applying electromotive force, nanofiber product manufacturing device 200 can be given injection unit 210 and passive electrode 220 charge inducings, thereby and can produce electric field.
In addition, solid inorganic material can be blended in the polymer.Solid inorganic material is used for the nanofiber that produces for example as granule (aggregate), and as the solvent that carries by nanofiber.The instance of solid inorganic material comprises: oxide, carbide, nitride, boride, silicide, fluoride, sulfhydrate.What be fit to is to use oxide aspect the heat-resisting and easy property handled.
The instance of oxide comprises: Al 2O 3, SiO 2, TiO 2, Li 2O, Na 2O, MgO, CaO, SrO, BaO, B 2O 3, P 2O 5, SnO 2, ZrO 2, K 2O, Cs 2O, ZnO, Sb 2O 3, As 2O 3, CeO 2, V 2O 5, Cr 2O 3, MnO, Fe 2O 3, CoO, NiO, Y 2O 3, Lu 2O 3, Yb 2O 3, HfO 2, Nb 2O 5One of them kind can be used, but alternatives is not limited thereto.
Deposition lamella 360 is such parts, and the nanofiber 400 that in predetermined space, produces deposits above that, and is flexible thin continuous lamella, can be separated easily by the nano-fiber film that the nanofiber of deposition is processed.Deposition lamella 360 is rolled-up and with the roll-good form supply.The part that delivery unit 370 is carried deposition lamella 360, above that, nanofiber deposits along the direction shown in Fig. 3 arrow.Lamella 360 is rolled with the bondedfibre fabric 410 that on deposition lamella 360, produces again.
Delivery unit 370 is such devices, makes roller shown in Figure 3 rotate through utilizing the motor (not shown), and it can transmit said deposition lamella 360 along a direction, keeps predetermined tensioning.
Should be noted that injection unit 210 and passive electrode 220 have various distortion, and have these multiple combination.Among Fig. 3, injection unit 210 schematically shows through the length dotted line that replaces with passive electrode 220, and the concrete distortion of injection unit 210 and passive electrode 220 describes below.
The figure of Fig. 4 shows the instance of injection unit 210 and passive electrode 220.
It is clearer to should be noted that thereby injection unit 210 amplifies the relation that makes between injection unit 210 and the passive electrode 220 in Fig. 4.In fact, the diameter of rotating cylinder 216 approximately is several centimetres to tens of centimetres, and the diameter of passive electrode 220 is several meters.
Passive electrode 220 is columns, and can rotate with the synchronized movement of deposition lamella 360.Passive electrode 220 has the marginal portion of cylindricality, can carry out circular chamfering on it, thereby the diameter of passive electrode 220 reduces gradually towards the edge.
The surface of the peripheral part of passive electrode 220 is away from 210 bendings of (against) injection unit, thereby prevents that electric field from being interfered by the edge.This feasible fabulous deposition that can produce nanofiber 400.
Like Fig. 4, injection unit 210 is such devices, and it utilizes centrifugal force spraying polymer (perhaps make polymer flow).Injection unit 210 comprises: rotating cylinder 216; Axle 217 is rotations, and as pipeline 211, is used for supply of polymer 400; Motor 218; Base portion 219; Be with 215; With belt wheel 214.
Rotating cylinder 216 comprises injection nozzle 213, is provided with radial mode.These nozzles 213 comprise the spray-hole 212 on the perisporium that is positioned at the rotating cylinder 216 with blind end.Rotating cylinder 216 has the other end, and connecting axle 217 therebetween.Rotating cylinder 216 is connected to pedestal 219 through axle 217, thereby it can rotate.
Motor 218 is with 215 to be connected with belt wheel 214 utilizations on being fixed on axle 217, and motor 218 is connected to pedestal 219.In this structure, the rotation of motor 218 makes rotating cylinder 216 with respect to pedestal 219 rotations.
Axle 217 is connected to other edge of rotating cylinder 216, thereby fluid can pass axle 217 inner and rotating cylinders 216.Axle 217 is processed by conductor with rotating cylinder 216.Axle 217 is connected to first power supply 250 through brush (brush).Brush makes can keep predetermined potential, even when rotating cylinder 216 rotations.
Rotating cylinder 216 is connected to storage box 107 through axle 217, and wherein the store aggregated thing 400.Pump is connected on the path, polymer 400 through this path by feed, and pump with polymer 400 towards rotating cylinder 216 pumpings.
The method that is used to make the nanofiber product that nanofiber 400 processes is described below; Be used for using with nanofiber product manufacturing device 200; This equipment comprises injection unit 210 and passive electrode 220, and describes the method that is used for making through the nanofiber 400 of deposition manufacturing bondedfibre fabric.
At first, polymer 400 216 pumpings from storage box 107 towards rotating cylinder.Among this embodiment, pumping pressure is low relatively, because polymer 400 is sprayed, does not use pumping pressure.
Polymer 400 is injected into rotating cylinder 216 inside through axle 217 (pipelines 211).Rotating cylinder 216 is through motor 218 rotations, is rotated in the polymer 400 of injection and produces centrifugal force.Through centrifugal force, polymer 400 is injected into outside the rotating cylinder 216 through spray-hole 212 with radial mode, and this spray-hole pierces through in the perisporium of rotating cylinder 216.
Because polymer 400 is sprayed through the spray-hole 212 in the rotating cylinder 216 of rotation, polymer 400 is ejected on the whole surface in the space through spray-hole 212 equably, though on some degree of shape of spray-hole 212 not simultaneously.The use of above-mentioned injection unit 210 makes can make quite a large amount of nanofiber 400, has equal in quality at every turn.This makes can make bondedfibre fabric 410, and wherein nanofiber is evenly dispersed.
Second source 251 applies voltage to passive electrode 220, and this voltage is defined in following one of them scope: from positive 10KV to positive 200KV; And from bearing 10KV to negative 200KV.In the rotating cylinder 216 of ground connection, and electric field (power line) is created between rotating cylinder 216 and the passive electrode 220 according to the charge generation of the voltage induced of passive electrode 220.
In this state, polymer 400 sprays from rotating cylinder 216.Produce the required electric charge of a series of electrostatic bursts and be applied to polymer 400.The particulate of polymer 400 dances in the air along electric field (power line), and the electrostatic burst of generation order, produces nanofiber 400.
Here, polymer 400 contains the high polymer particulate of swelling, and wherein, hydrone is present between the polymer molecule.Therefore, the volume of polymer 400 of high polymer particulate that comprises swelling is greater than the volume of the polymer that does not contain any swelling polymer particles.With the polymer phase ratio that does not contain this swelling polymer particles, the polymer 400 that contains the swelling polymer particles can keep more a large amount of electric charges.Along with the water evaporation, the electric charge that applies penetrates the micro polymer intragranular of polymer 400 deeply, and the electrostatic burst of generation order, and like this, the combination of polymers molecule is separated from each other.Therefore, use the polymer 400 for preparing through this method to make and to produce nanofiber, do not use any organic solvent.
The nanofiber 400 that produces is deposited on the said deposition lamella 360, and deposition lamella 360 is rolled gradually, on deposition lamella 360, produces continuous bondedfibre fabric.
Among this embodiment, can confirm that injection unit 210 has earth potential, but arbitrarily output voltage for example the voltage from negative 1KV to positive 1KV can be applied to injection unit 210.
Fig. 4 shows single injection unit 210, but in the situation of using wide deposition lamella 360, perhaps increases the thickness of nano-fiber film, effectively uses a plurality of injection units 210 that are provided with certain mode.
The structure that should be noted that injection unit 210 is not limited to the structure that present embodiment is described.For example, like Fig. 5, nozzle 213 can be fixing with respect to passive electrode 220.In this situation, a plurality of nozzles 213 are set diagonally through the direction of motion with respect to deposition lamella 360, the interval that can widen each nozzle 213, and nanofiber 400 is deposited on the said deposition lamella 360 equably.
The distortion of fine polymer manufacturing equipment is described below.
The fine polymer manufacturing equipment 100 of Fig. 6 comprises: transfer pump 136 again, are used for the polymer of storage box 107 storages is fed to receiving magazine 103 again; Transport path 132 again.
Utilize this structure, can and and then in solvent, make polymer particulates become meticulousr and swelling so that deposition is even again with the polymer that becomes piece.
Like Fig. 7, can carry out processes in addition: to the inorganic material of hopper 131 feed polymer and granular form; Utilize agitator to stir polymer and inorganic material, for example diaxon is extruded device 130 etc., utilizes heater 104 heated polymerizable thing and inorganic material simultaneously; With polymer is discharged through first outlet 111.
In addition, inwardly projecting orifice 110 and external nozzles 120 can ground connection, and as injection unit 210.In this situation; Polymer particulates becomes meticulousr and swelling in superheated steam; And the nozzle that mixes from solution-air flies out; And the inwardly projecting orifice 110 of ground connection applies electrode with external nozzles 120 as electric charge, is used to apply electric charge to being passed through the polymer that inwardly projecting orifice 110 and external nozzles 120 are discharged.Fly the electrostatic burst of generation order in the electric field that produces between polymer particulates each in having high-tension passive electrode 220 and inwardly projecting orifice 110, external nozzles 120.
Utilize this structure, processing that can execution sequence begins with the feed polymer, and finishes to produce the nanofiber product.
Not not with an organic solvent, should be noted that still the present invention not exclusively gets rid of with an organic solvent in the present embodiment.The organic solvent of appropriate amount can be used for the viscosity of telomerized polymer or is used for other purpose as required.
The invention discloses and utilize water to do solvent and superheated steam to come emulsification or accurate Emulgating polymers, be not limited to these but be used for producing the material that the original solution (raw solution) of nanofiber contains.For example, original solution can come emulsification or accurate emulsification through the nozzle that uses solution-air to mix, only do not use superheated steam, depends on the type of polymer.Be concrete instance below.How polymer for example polyvinyl alcohol (PVA) is dissolved in the water and changes according to saponification degree.Therefore, depend on the saponification degree with the polymer that is used, can make original solution, wherein, polyvinyl alcohol (PVA) by emulsification or accurate emulsification, but does not use superheated steam through the equipment that uses Fig. 1 structure.
Make the method for the water soluble (CO) polymers emulsification be used to produce nanofiber be not limited thereto.Utilize the method for agitator, colloid mill, homogenizer etc. to can be used for making emulsifying polymers or accurate emulsifying polymers, thereby utilize the polymer of making to produce nanofiber.
Should be noted that between Emulgating polymers and accurate Emulgating polymers and do not have obvious limit.For example, when polymer particulates is continued predetermined amount of time by emulsification, but along with the time goes over, particle deposition or dissolving subsequently, this polymer can be described as accurate Emulgating polymers.
Though only describe exemplary embodiments of the present invention above in detail, one skilled in the art will know that, do not breaking away from essence under the situation of novel teachings of the present invention and advantage, can make multiple variation to exemplary embodiments.Therefore, all this variations all drop in the scope of the invention.
Instance
Embodiment according to the present invention is described below, compares with existing instance.
(utilizing the test 1 of commonsense method)
At first, the original solution that is used to produce nanofiber utilizes following method to produce.
Polyvinyl alcohol (PVA) and water (running water) are prepared, respectively as polymer and solvent.
Through PVA and water are fed in the container, stir with 10 to 90 volume ratio of institute's listed sequence, the liquid of mixing produces.
Through using agitator, mixing material is by mixing.
Through said process, produce following original solution: original solution stirred 24 hours; Original solution stirred 36 hours; Original solution stirred 48 hours.
Simultaneously, be used to produce the method generation of original solution through utilizing fine polymer manufacturing equipment shown in Figure 6 100 bases to describe below of nanofiber.
Liquid PVA (under the room temperature) is pumped, and discharges through first outlet 111.
Superheated steam (having 300 degrees centigrade temperature) is discharged through second outlet 121.
Liquid PVA and superheated steam are discharged with being repeated, and the liquid of collecting in the storage box 107 simultaneously is recycled.
Through said process, produce following original solution: original solution, circulated 10 minutes; Original solution circulated 20 minutes; And original solution, circulated 30 minutes.
These original solutions are respectively applied for through using fine polymer manufacturing equipment 100 to produce nanofiber.Stir 48 hours original material and 30 minutes the original solution of circulation through utilizing fine polymer manufacturing equipment 100 circulation combination results contain the nanofiber of fabulous PVA.Test 1 demonstrates through the original solution that contains PVA that uses superheated steam and produce at short notice and produces fabulous nanofiber.
(utilizing test 2 of the present invention)
Nylon and formic acid are prepared as polymer and solvent respectively.
Stir through nylon and formic acid are fed in the container, produce the liquid that mixes, the volume ratio of listed order is 10 to 90.
The liquid that mixes stirs the wing through use and is stirred.
Through said process, produce following original solution: original solution stirred 24 hours; Original solution stirred 36 hours; Original solution stirred 48 hours.
Simultaneously, be used to produce the method generation of original solution through utilizing fine polymer manufacturing equipment shown in Figure 6 100 bases to describe below of nanofiber.
The mixing material that contains formic acid and nylon is pumped and discharges through first outlet 111, and nylon is by fragmentation (crashed) and be dispersed in the formic acid.
Superheated steam (having 300 degrees centigrade temperature) is discharged through second outlet 121.
Mixing material and superheated steam are discharged with being repeated, and the liquid of collecting in the storage box 107 simultaneously is recycled.
Through said process, produce following original solution: original solution, circulated 10 minutes; Original solution circulated 20 minutes; And original solution, circulated 30 minutes.The volume of each original solution is measured, and measures and to demonstrate, and the ratio of formic acid approximately drops to 70% from 90% in the whole original solution.
These original solutions are respectively applied for through using fine polymer manufacturing equipment 100 to produce nanofiber.Stir 48 hours original material and the combination results through utilizing 30 minutes original solution of fine polymer manufacturing equipment 100 circulation and contained the nanofiber of fabulous nylon.Test 2 demonstrates fabulous nanofiber and produces through following manner: through nylon and formic acid are mixed to obtain to contain the mixing material of nylon and formic acid, with the mixing material pumping, discharge mixing material and superheated steam.In addition, test 2 demonstrates the feasible amount that can greatly reduce solvent of this method.Therefore, need in the situation of resin of a large amount of expensive solvent in use, this method is effective.
As above, among the present invention, the polymer of discharging from first outlet is in such form equally: polymer dissolution is in organic solvent.In this situation, be mixed in combination of polymers and the organic solvent, therefore make it possible to emulsification from the hydrone of superheated steam.As a result, make nanofiber through utilizing emulsifying liquid, the amount of the organic solvent that is used is greatly reduced, effect is very significant.In addition, stable original solution produces at short notice, so manufacture process also can shorten.
Industrial applicibility
The present invention can be used for having in the field of low viscous polymer, particularly can be used for producing nanofiber and is used to make fibre spinning and bondedfibre fabric, and nanofiber is used for it.

Claims (2)

1. method that is used to make fine polymer, this method comprises:
Produce superheated steam, said generation step is carried out through the superheated steam generation unit;
Be adjusted in the pressure of the superheated steam that produces in the said generation step, said regulating step carries out through pressure regulating unit;
Reception is used to make the polymer of nanofiber, and said receiving step carries out through receiving element;
The polymer that receives in the said receiving step is heated to predetermined temperature, and said heating steps carries out through heating unit;
The polymer that will have after the heating of predetermined temperature is discharged through first outlet;
With the discharge of carrying out said polymer simultaneously, superheated steam is discharged through second outlet, second outlet is around first outlet, and first outlet and second outlet are towards equidirectional; With
To discharge the step of polymer and be stored in the storage box together with water through first outlet through the polymer that second outlet is discharged the meticulous swelling of step of superheated steam.
2. the method that is used to make fine polymer as claimed in claim 1 is characterized in that, said method also comprises:
The fine polymer of discharging in the discharge step with said fine polymer is fed to receiving element again.
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